Chamara Abeysekera

Broadband multi-resonant strong field coherence breaking as a tool for single isomer microwave spectroscopy

Using standard hardware available in chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy, an experimental method is introduced to selectively extract from the microwave spectrum of an otherwise complicated multicomponent mixture a set of transitions due to a single component, thereby speeding spectral assignment. The method operates the broadband chirped-pulse used to excite the sample in the strong-field limit through a combination of high power and control of the sweep rate. A procedure is introduced that leads to selection of three transition frequencies that can be incorporated as a set of resonant sequential single-frequency microwave pulses that follow broadband chirped-pulse excitation, resulting in a reduction in the coherent signal from a set of transitions ascribable to the component of interest. The difference in the CP-FTMW spectrum with and without this set of multi-resonant single-frequency pulses produces a set of transitions that can confidently be assigned to a single compone...

Broadband Microwave Spectroscopy of 2-Furanyloxy Radical: Primary Pyrolysis Product of the Second-Generation Biofuel 2-Methoxyfuran

Broadband microwave spectra over the 2-18 GHz range have been recorded for the resonance-stabilized 2-furanyloxy radical, formed in the first step of pyrolysis of the second-generation biofuel 2-methoxyfuran by methyl loss. Using a flash pyrolysis source attached to a pulsed valve, a 0.7% mixture of 2-methoxyfuran in argon was pyrolyzed at a series of temperatures ranging from 300 to 1600 K. Subsequent cooling in a supersonic expansion produced rotational temperatures of ∼2 K in the interrogation region. Using chirped-pulse Fourier transform microwave (CP-FTMW) methods, combined with strong-field coherence breaking (SFCB), a set of transitions due to the radical were identified and assigned. The experimental rotational constants ( A = 8897.732(93), B = 4019.946(24), C = 2770.321(84)), centrifugal distortion constants, and spin-rotation coupling constants have been determined for the radical and compared with ab initio predictions at the CCSD(T) level of theory. Compared to the 2-methoxyfuran precursor, the 2-furanyloxy radical has allylic C-C bond lengths intermediate between single and double bonds, a shortened C(5)-O(6) bond characteristic of partial double-bond character, and an O(1)-C(5)-O(6) bond angle of 121°, which resembles the O-C-O angle of an ester. Atomic spin densities extracted from the calculations confirm that the 2-furanyloxy radical is best viewed as a carbon-centered allylic lactone radical, with 80% of the spin density on the two allylic carbons and 20% on the pendant O(6) atom.

Multiplexed characterization of complex gas-phase mixtures combining chirped-pulse Fourier transform microwave spectroscopy and VUV photoionization time-of-flight mass spectrometry

We report details of the design and operation of a single apparatus that combines Chirped-Pulse Fourier Transform Microwave (CP-FTMW) spectroscopy with vacuum ultraviolet (VUV) photoionization Time-of-Flight Mass Spectrometry (TOFMS). The supersonic expansion used for cooling samples is interrogated first by passing through the region between two microwave horns capable of broadband excitation and detection in the 2-18 GHz frequency region of the microwave. After passing through this region, the expansion is skimmed to form a molecular beam, before being probed with 118 nm (10.5 eV) single-photon VUV photoionization in a linear time-of-flight mass spectrometer. The two detection schemes are powerfully complementary to one another. CP-FTMW detects all components with significant permanent dipole moments. Rotational transitions provide high-resolution structural data. VUV TOFMS provides a gentle and general method for ionizing all components of a gas phase mixture with ionization thresholds below 10.5 eV, providing their molecular formulae. The advantages, complementarity, and limitations of the combined methods are illustrated through results on two gas-phase mixtures made up of (i) three furanic compounds, two of which are structural isomers of one another, and (ii) the effluent from a flash pyrolysis source with o-guaiacol as the precursor.